Fixed-Point Atomic Regulation Engineered Low-Thickness Wideband Microwave Absorption.

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12 GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7 mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8 GHz, RLmin = -46 dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

Functional nanoporous graphene superlattice.

Two-dimensional (2D) superlattices, formed by stacking sublattices of 2D materials, have emerged as a powerful platform for tailoring and enhancing material properties beyond their intrinsic characteristics. However, conventional synthesis methods are limited to pristine 2D material sublattices, posing a significant practical challenge when it comes to stacking chemically modified sublattices. Here we report a chemical synthesis method that overcomes this challenge by creating a unique 2D graphene superlattice, stacking graphene sublattices with monodisperse, nanometer-sized, square-shaped pores and strategically doped elements at the pore edges. The resulting graphene superlattice exhibits remarkable correlations between quantum phases at both the electron and phonon levels, leading to diverse functionalities, such as electromagnetic shielding, energy harvesting, optoelectronics, and thermoelectrics. Overall, our findings not only provide chemical design principles for synthesizing and understanding functional 2D superlattices but also expand their enhanced functionality and extensive application potential compared to their pristine counterparts.

Wrinkle Structure Regulating Electromagnetic Parameters in Constructed Core-shell ZnFe2O4@PPy Microspheres as Absorption Materials.

Structure engineering of magnetic-dielectric multi-components is emerging as an effective approach for presuming high-performance electromagnetic (EM) absorption, but still faces bottlenecks due to the ambiguous regulation mechanism of surface morphology. Here, a novel wrinkled surface structure is tailored on the ZnFe2O4 microsphere via a spray-pyrolysis induced Kirkendall diffusion effect, the conductivity of the sample is affected, and a better impedance matching is adjusted by modulating the concentration of metal nitrate precursors. Driven by a vapor phase polymerization, conductive polypyrrole (PPy) shell are in situ decorated on the ZnFe2O4 microsphere surfaces, ingeniously constructing a core-shell ZnFe2O4@PPy composites. Moreover, a systematic investigation reveals that this unique wrinkled surface structure is highly dependent on the metal salt concentration. Optimized wrinkle ZnFe2O4@PPy composite exhibits a minimum reflection loss (RLmin) reached -41.0 dB and the effective absorption bandwidth (EAB) can cover as wide as 4.1 GHz. The enhanced interfacial polarization originated from high-density ZnFe2O4-PPy heterostructure, and the conduction loss of PPy contributes to the boosted dielectric loss capability. This study gives a significant guidance for preparing high-performance EM composites by tailoring the surface wrinkle structure.

A polymer tethering strategy to achieve high metal loading on catalysts for Fenton reactions.

The development of heterogenous catalysts based on the synthesis of 2D carbon-supported metal nanocatalysts with high metal loading and dispersion is important. However, such practices remain challenging to develop. Here, we report a self-polymerization confinement strategy to fabricate a series of ultrafine metal embedded N-doped carbon nanosheets (M@N-C) with loadings of up to 30 wt%. Systematic investigation confirms that abundant catechol groups for anchoring metal ions and entangled polymer networks with the stable coordinate environment are essential for realizing high-loading M@N-C catalysts. As a demonstration, Fe@N-C exhibits the dual high-efficiency performance in Fenton reaction with both impressive catalytic activity (0.818 min-1) and H2O2 utilization efficiency (84.1%) using sulfamethoxazole as the probe, which has not yet been achieved simultaneously. Theoretical calculations reveal that the abundant Fe nanocrystals increase the electron density of the N-doped carbon frameworks, thereby facilitating the continuous generation of long-lasting surface-bound •OH through lowering the energy barrier for H2O2 activation. This facile and universal strategy paves the way for the fabrication of diverse high-loading heterogeneous catalysts for broad applications.

High-Entropy Enhanced Microwave Attenuation in Titanate Perovskites.

High-entropy oxides (HEOs), which incorporate multiple-principal cations into single-phase crystals and interact with diverse metal ions, extend the border for available compositions and unprecedented properties. Herein, a high-entropy-stabilized (Ca0.2 Sr0.2 Ba0.2 La0.2 Pb0.2 )TiO3  perovskite is reported, and the effective absorption bandwidth (90% absorption) improves almost two times than that of BaTiO3 . The results demonstrate that the regulation of entropy configuration can yield significant grain boundaries, oxygen defects, and an ultradense distorted lattice. These characteristics give rise to strong interfacial and defect-induced polarizations, thus synergistically contributing to the dielectric attenuation performance. Moreover, the large strains derived from the strong lattice distortions in the high-entropy perovskite offer varied transport for electron carriers. The high-entropy-enhanced positive/negative charges accumulation around grain boundaries and strain-concentrated location, quantitatively validated by electron holography, results in unusual dielectric polarization loss. This study opens up an effective avenue for designing strong microwave absorption materials to satisfy the increasingly demanding requirements of advanced and integrated electronics. This work also offers a paradigm for improving other interesting properties for HEOs through entropy engineering.

CuCo2O4 supported on activated carbon as a novel heterogeneous catalyst with enhanced peroxymonosulfate activity for efficient removal of organic pollutants.

CuCo2O4 was synthesized via a relatively simple method, and innovatively supported onto the activated carbon (AC) by calcination to obtain a novel heterogeneous catalyst (AC-CuCo2O4). Brilliant red 3BF (3BF) was selected as the probe compound to investigate the catalytic activity of AC-CuCo2O4 in the presence of peroxymonosulfate (PMS). The results showed that 98% removal rate could be achieved and the reaction rate constant (0.476 min-1) was 5.2 times greater than that of CuCo2O4 alone (0.091min-1), suggesting that the introduction of AC could greatly enhance the catalytic activity of pure CuCo2O4. Typically, the 3BF removal was as high as 96% after five cycles, showing the good stability of catalyst reuse. Additionally, the effects of the initial pH, catalyst dosage, PMS concentration and reaction temperature on the 3BF removal were investigated, demonstrating that AC-CuCo2O4 effectively remove 3BF over a wide pH range (5.0-10.0) and possessed temperature-tolerant performance. To further explore the 3BF removal mechanism, electron paramagnetic resonance technology combining with trapping agents was employed to confirm the involvement of reactive oxygen species including SO4•-, •OH, O2•- and 1O2, which distinctly differed from the reported CuCo2O4 for PMS activation. These findings provided an addition promising strategy in environmental remediation.

Phosphorus-doped carbon fibers as an efficient metal-free bifunctional catalyst for removing sulfamethoxazole and chromium (VI).

Developing an efficient and metal-free bifunctional catalyst for the simultaneous degradation of antibiotic and reduction of Cr (VI) has been regarded as increasingly attractive yet challenging objectives in the environmental catalysis field. Herein, phosphorus-doped carbon fibers (P-CFs) was innovatively prepared by doping and calcination methods, characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Sulfamethoxazole (SMX) as the target contaminant was selected to evaluate the catalytic activity of P-CFs in PMS activation, over 90% SMX removal and 82.75% mineralization were high-efficiently achieved in the P-CFs/peroxymonosulfate (PMS) system. Particularly, P-CFs/PMS system exhibited a superior catalytic oxidation performance over a wide pH range (3.5-9.5) and even in the complicated water matrix. Surprisingly, the presence of humic acid (HA) in the P-CFs/PMS system could achieve about 2 times enhancement on SMX removal, different from most reports about the inhibition of HA in PMS activation. More importantly, Brunauer-Emmett-Teller (BET) method and XPS analysis revealed that the highly toxic Cr (VI) could be reduced to Cr (III) by P-CFs. Furthermore, electron spin resonance (ESR) combined with various trapping agents demonstrated that SO4•-, •OH and 1O2. were generated and participated in the SMX degradation, while the free electron in P-CFs played a main role in Cr (VI) reduction. This finding not only provided a high-efficiency strategy in the treatment of wastewaters containing organic contaminants and heavy metals Cr (VI), but might open new insights into an innovative metal-free catalyst in environment remediation.

Highly efficient removal of organic pollutants via a green catalytic oxidation system based on sodium metaborate and peroxymonosulfate.

The development of highly efficient and green catalytic oxidation process based on peroxymonosulfate (PMS) activation has been identified to be a significant yet challenging objective in the environmental catalysis field. A simple, environmentally benign and highly effective catalytic oxidation system was innovatively constructed by coupling NaBO2 and PMS for the removal of Acid Red 1. The catalytic mechanism in the NaBO2/PMS system was elucidated by electron paramagnetic resonance (EPR) combined with several radical capture reagents (ascorbic acid, methanol, tert-butyl alcohol, ethanol and l-histidine). The experimental results indicated that singlet oxygen (1O2) severed as the predominant reactive oxygen species (ROS) rather than the HO or during the catalytic oxidation process, at variance with the reported radical pathway in the Co2+/PMS system. Inspiringly, p-benzoquinone (p-BQ) as a trapping agent in most advanced oxidation process could be turned into the positive one in the NaBO2/PMS system, achieving a nearly 3-times enhancement in terms of the rate constant for AR1 removal. More interestingly, sodium chloride (NaCl) presented the same enhancement effect as p-benzoquinone due to generation of hypochlorous acid (HOCl) and more 1O2, which was completely different from the reported. This study develops a highly efficient green oxidation process and opens up a new insight in the remediation of contaminated water.